JP6636596B2 - In-cell type liquid crystal panel and liquid crystal display device - Google Patents

Description

  The present invention relates to an in-cell type liquid crystal cell having a touch sensing function incorporated in a liquid crystal cell, and an in-cell type liquid crystal panel having a polarizing film with an adhesive layer on the viewing side of the in-cell type liquid crystal cell. Further, the present invention relates to a liquid crystal display device using the liquid crystal panel. The liquid crystal display device with a touch sensing function using the in-cell type liquid crystal panel of the present invention can be used as various input display devices such as mobile devices.

  In general, a liquid crystal display device has polarizing films bonded to both sides of a liquid crystal cell via an adhesive layer due to its image forming method. In addition, a liquid crystal display device having a display screen equipped with a touch panel has been put to practical use. As the touch panel, there are various types such as a capacitive type, a resistive type, an optical type, an ultrasonic type and an electromagnetic induction type, and the capacitive type is increasingly used. In recent years, a liquid crystal display device with a touch sensing function having a built-in capacitance sensor as a touch sensor unit has been used.

  On the other hand, at the time of manufacturing a liquid crystal display device, when the polarizing film with an adhesive layer is attached to a liquid crystal cell, the release film is peeled from the adhesive layer of the polarizing film with an adhesive layer. Separation generates static electricity. Also, static electricity is generated when the surface protective film of the polarizing film attached to the liquid crystal cell is peeled off or when the surface protective film of the cover window is peeled off. The static electricity generated in this way affects the orientation of the liquid crystal layer inside the liquid crystal display device, and causes a defect. Generation of static electricity can be suppressed, for example, by forming an antistatic layer on the outer surface of the polarizing film.

On the other hand, the capacitance sensor in the liquid crystal display device with a touch sensing function detects a weak capacitance formed by the transparent electrode pattern and the finger when the user's finger approaches the surface. When a conductive layer such as an antistatic layer is provided between the transparent electrode pattern and the user's finger, the electric field between the driving electrode and the sensor electrode is disturbed, and the sensor electrode capacitance is destabilized and the touch panel sensitivity is reduced. , Which may cause malfunction. In a liquid crystal display device with a touch sensing function, it is required to suppress the generation of static electricity and the malfunction of the capacitance sensor. For example, in order to reduce the occurrence of display defects and malfunctions in a liquid crystal display device with a touch sensing function, the surface resistance of the liquid crystal display device with a touch sensing function is 1.0 × 10 ^{9 to} 1.0 × 10 ¹¹ Ω / □. It has been proposed to arrange a polarizing film having an antistatic layer on the viewing side of a liquid crystal layer (Patent Document 1).

JP 2013-105154 A

  According to the polarizing film having the antistatic layer described in Patent Literature 1, it is possible to suppress generation of static electricity to some extent. However, in Patent Literature 1, since the location of the antistatic layer is farther than the fundamental position where static electricity is generated, it is less effective than the case where an antistatic function is provided to the adhesive layer. In addition, in a liquid crystal display device with a touch sensing function using an in-cell type liquid crystal cell, by providing a conductive structure on the side surface of the polarizing film, conductivity can be provided from the side surface, but when the antistatic layer is thin, It was found that, because of the small contact area with the conductive structure on the side surface, sufficient conductivity could not be obtained and poor conduction occurred. On the other hand, it was found that when the antistatic layer became thicker, the sensitivity of the touch sensor was lowered.

  On the other hand, the pressure-sensitive adhesive layer provided with an antistatic function is more effective than an antistatic layer provided on the polarizing film in suppressing static electricity generation and preventing static electricity unevenness. However, it was found that if the antistatic function of the pressure-sensitive adhesive layer was regarded as important and the conductive function of the pressure-sensitive adhesive layer was enhanced, the touch sensor sensitivity was reduced. In particular, it has been found that the touch sensor sensitivity is reduced in a liquid crystal display device with a touch sensing function using an in-cell type liquid crystal cell. In addition, the antistatic agent added to the pressure-sensitive adhesive layer to enhance the conductive function may segregate at the interface with the polarizing film in a humid environment (after the humidification reliability test) or may occur at the viewing side interface of the liquid crystal cell. And it was found that the durability was not sufficient.

  The present invention is an in-cell type liquid crystal panel having an in-cell type liquid crystal cell and a polarizing film with a pressure-sensitive adhesive layer applied to the viewing side thereof, which has a good antistatic function, and a touch sensor sensitivity, in a humid environment. It is an object of the present invention to provide an in-cell type liquid crystal panel which can satisfy the durability of the present invention.

  Another object of the present invention is to provide a liquid crystal display device using the in-cell type liquid crystal panel.

  The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the following problems can be solved by the following in-cell type liquid crystal panel, and have completed the present invention.

That is, the present invention provides a liquid crystal layer containing liquid crystal molecules that are homogeneously aligned in the absence of an electric field, a first transparent substrate and a second transparent substrate sandwiching the liquid crystal layer on both sides, and the first transparent substrate and the second transparent substrate. In-cell type liquid crystal cell having a touch sensing electrode portion according to a touch sensor and a touch drive function between the substrate,
An in-cell type liquid crystal panel having a polarizing film with an adhesive layer disposed on a first transparent substrate side on a viewing side of the in-cell type liquid crystal cell without a conductive layer via a first adhesive layer,
The pressure-sensitive adhesive layer-attached polarizing film has a first polarizing film, an anchor layer, and a first pressure-sensitive adhesive layer in this order,
The invention relates to an in-cell type liquid crystal panel, wherein the anchor layer contains a conductive polymer, and the first pressure-sensitive adhesive layer contains an antistatic agent.

  In the in-cell type liquid crystal panel, a conductive structure may be provided on a side surface of the anchor layer and the first adhesive layer of the polarizing film with the adhesive layer.

In the in-cell liquid crystal panel, the anchor layer has a thickness of 0.01 to 0.5 μm and a surface resistance of 1 × 10 ⁸ to 1 × 10 ¹² Ω / □,
The first pressure-sensitive adhesive layer has a thickness of 5 to 100 μm, a surface resistance of 1 × 10 ⁸ to 1 × 10 ¹² Ω / □, and
It is preferable that the surface resistance value of the pressure-sensitive adhesive layer side of the polarizing film with the pressure-sensitive adhesive layer is 1 × 10 ⁸ to 1 × 10 ¹¹ Ω / □.

  In the in-cell type liquid crystal panel, an alkali metal salt and / or an organic cation-anion salt can be contained as the antistatic agent.

  In the in-cell type liquid crystal panel, the touch sensing electrode unit may be disposed between the liquid crystal layer and the first transparent substrate or the second transparent substrate. The touch sensing electrode unit may be one that is disposed between the liquid crystal layer and the first transparent substrate, and one that is disposed between the liquid crystal layer and the second transparent substrate. Can be used.

  In the in-cell type liquid crystal panel, the touch sensing electrode portion may be formed of a touch sensor electrode and a touch drive electrode.

  In the in-cell type liquid crystal panel, when the touch sensing electrode unit is disposed between the liquid crystal layer and the first transparent substrate or the second transparent substrate, the touch sensing electrode unit includes a touch sensor electrode and a touch driving electrode. An electrode in which an electrode is integrally formed can be used.

  The in-cell type liquid crystal panel may include a second polarizing film disposed on a side of the second transparent substrate of the in-cell type liquid crystal cell via a second adhesive layer.

  The invention also relates to a liquid crystal display device having the in-cell type liquid crystal panel.

  The polarizing film with a pressure-sensitive adhesive layer on the viewing side in the in-cell type liquid crystal panel of the present invention, since the anchor layer contains a conductive polymer, the pressure-sensitive adhesive layer contains an antistatic agent and has an antistatic function, In the in-cell type liquid crystal panel, when the conductive structure is provided on each side of the anchor layer and the pressure-sensitive adhesive layer, the conductive structure can be brought into contact with the conductive structure, and the contact area can be sufficiently secured. Therefore, conduction on the side surfaces of each of the anchor layer and the pressure-sensitive adhesive layer is ensured, and occurrence of static electricity unevenness due to poor conduction can be suppressed.

  Further, the polarizing film with a pressure-sensitive adhesive layer of the present invention, the surface resistance of each layer of the anchor layer and the pressure-sensitive adhesive layer is controlled to a predetermined range, and, on the pressure-sensitive adhesive layer side of the polarizing film with a pressure-sensitive adhesive layer. Can be controlled so as to be within a predetermined range. As described above, the pressure-sensitive adhesive layer-attached polarizing film of the present invention can control the surface resistance of the anchor layer and the pressure-sensitive adhesive layer while controlling so that the touch sensor sensitivity is not lowered or the durability in a humid environment is not deteriorated. And a predetermined antistatic function can be imparted. Therefore, the polarizing film with a pressure-sensitive adhesive layer of the present invention can satisfy touch sensor sensitivity and durability in a humid environment while having a good antistatic function.

It is sectional drawing which shows an example of the polarizing film with an adhesive layer used for the viewing side of the in-cell type liquid crystal panel of this invention. 1 is a cross-sectional view illustrating an example of an in-cell type liquid crystal panel of the present invention. 1 is a cross-sectional view illustrating an example of an in-cell type liquid crystal panel of the present invention. 1 is a cross-sectional view illustrating an example of an in-cell type liquid crystal panel of the present invention. 1 is a cross-sectional view illustrating an example of an in-cell type liquid crystal panel of the present invention. 1 is a cross-sectional view illustrating an example of an in-cell type liquid crystal panel of the present invention.

  Hereinafter, the present invention will be described with reference to the drawings. As shown in FIG. 1, the polarizing film A with an adhesive layer used on the viewing side of the in-cell liquid crystal panel of the present invention has a first polarizing film 1, an anchor layer 3, and a first adhesive layer 2 in this order. Further, a surface treatment layer 4 may be provided on the side of the first polarizing film 1 where the anchor layer 3 is not provided. FIG. 1 illustrates a case where the polarizing film A with an adhesive layer has a surface treatment layer 4. The polarizing film A with a pressure-sensitive adhesive layer of the present invention is arranged on the transparent substrate 41 side of the in-cell type liquid crystal cell B shown in FIGS. Although not shown in FIG. 1, a separator can be provided on the first pressure-sensitive adhesive layer 2 of the polarizing film A with a pressure-sensitive adhesive layer of the present invention, and the surface treatment layer 4 (having no surface treatment layer 4) can be provided. In such a case, the first polarizing film 1) can be provided with a surface protective film.

The thickness of the anchor layer 3 is preferably 0.01 to 0.5 μm, and more preferably 0.01 to 0.2 μm, from the viewpoint of stability of the surface resistance value and adhesion to the pressure-sensitive adhesive layer. Preferably, it is more preferably 0.01 to 0.1 μm. Also, the surface resistance of the anchor layer 3 from the viewpoint of antistatic function and the touch sensor ^{sensitivity, 1 × 10 8 ~1 × 10} 12 Ω / □ is preferably ^{from, 1 × 10 8 ~1 × 10} 11 Ω / □, more preferably 1 × 10 ⁸ to 1 × 10 ¹⁰ Ω / □.

The thickness of the first pressure-sensitive adhesive layer 2 is preferably from 5 to 100 μm, more preferably from 5 to 50 μm, further preferably from 10 to 35 μm, from the viewpoint of ensuring durability and ensuring a contact area with the side surface conductive structure. It is preferred that Also, the terms of the first surface resistance antistatic function and the touch sensor sensitivity of the pressure-sensitive adhesive layer ^{2, 1 × 10 8 ~1 ×} 10 12 Ω / □ is preferably from, 1 × ¹⁰ 8 to 1 × It is preferably 10 ¹¹ Ω / □, and more preferably 1 × 10 ⁸ to 1 × 10 ¹⁰ Ω / □.

Further, the surface resistance value of the pressure-sensitive adhesive layer 2 side in the pressure-sensitive adhesive layer-attached polarizing film A satisfies the antistatic function and lowers the touch sensor sensitivity so as not to lower the durability in a humid environment. It is preferably controlled to 1 × 10 ⁸ to 1 × 10 ¹¹ Ω / □. The surface resistance value can be adjusted by controlling the surface resistance values of the anchor layer 3 and the first pressure-sensitive adhesive layer 2 respectively. The surface resistance value is preferably from 1 × 10 ^{8 to} 6 × 10 ¹⁰ Ω / □, and more preferably from 1 × 10 ⁸ to 4 × 10 ¹⁰ Ω / □.

  Hereinafter, the polarizing film A with an adhesive layer will be described. As described above, the polarizing film A with the pressure-sensitive adhesive layer of the present invention has the first polarizing film 1, the anchor layer 3, and the first pressure-sensitive adhesive layer 2 in this order. In addition, a surface treatment layer 4 can be provided.

<First polarizing film>
As the first polarizing film, one having a transparent protective film on one or both sides of a polarizer is generally used. The polarizer is not particularly limited, and various types can be used. Examples of the polarizer include, for example, a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, a hydrophilic polymer film such as an ethylene-vinyl acetate copolymer-based partially saponified film, and dichroic properties of iodine and a dichroic dye. Examples thereof include a uniaxially stretched film obtained by adsorbing a substance, a polyene-based oriented film such as a dehydrated product of polyvinyl alcohol and a dehydrochlorination product of polyvinyl chloride. Among these, a polarizer composed of a polyvinyl alcohol-based film and a dichroic substance such as iodine is preferable. The thickness of these polarizers is not particularly limited, but is generally about 80 μm or less.

  As the polarizer, a thin polarizer having a thickness of 10 μm or less can be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. Such a thin polarizer preferably has a small thickness unevenness, is excellent in visibility, is small in dimensional change, is excellent in durability, and furthermore, is preferably thin in thickness as a polarizing film.

  As a material constituting the transparent protective film, for example, a thermoplastic resin having excellent transparency, mechanical strength, heat stability, moisture barrier properties, isotropy and the like is used. Specific examples of such a thermoplastic resin include cellulose resins such as triacetyl cellulose, polyester resins, polyether sulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, and cyclic resins. Examples include a polyolefin resin (a norbornene-based resin), a polyarylate resin, a polystyrene resin, a polyvinyl alcohol resin, and a mixture thereof. A transparent protective film is adhered on one side of the polarizer with an adhesive layer, and on the other side, a (meth) acrylic, urethane, acrylic urethane, epoxy, silicone A thermosetting resin such as a resin or an ultraviolet curable resin can be used. The transparent protective film may contain one or more optional appropriate additives.

  The adhesive used for laminating the polarizer and the transparent protective film is not particularly limited as long as it is optically transparent.Aqueous, solvent-based, hot-melt, radical-curable, and cation-curable types are used. However, water-based adhesives or radical-curable adhesives are preferred.

<Antistatic agent>
Examples of the antistatic agent include materials that can impart antistatic properties, such as ionic surfactants, conductive polymers, and conductive fine particles. An ionic compound can be used as the antistatic agent.

  Examples of the ionic surfactant include cationic (for example, quaternary ammonium salt type, phosphonium salt type, sulfonium salt type, etc.) and anionic type (carboxylic acid type, sulfonate type, sulfate type, phosphate type, phosphite type, etc.). , Zwitterionic (sulfobetaine type, alkylbetaine type, alkylimidazolium betaine type, etc.) or nonionic (polyhydric alcohol derivative, β-cyclodextrin inclusion compound, sorbitan fatty acid monoester / diester, polyalkylene oxide derivative, amine Oxides and the like).

  Examples of the conductive polymer include polyaniline-based, polythiophene-based, polypyrrole-based, and polyquinoxaline-based polymers. Of these, polyaniline and polythiophene, which are easily formed into a water-soluble conductive polymer or a water-dispersible conductive polymer. Are preferably used. Particularly, polythiophene is preferable.

  Examples of the conductive fine particles include metal oxides such as tin oxide, antimony oxide, indium oxide, and zinc oxide. Of these, tin oxide is preferred. Examples of the tin oxide-based material include, in addition to tin oxide, antimony-doped tin oxide, indium-doped tin oxide, aluminum-doped tin oxide, tungsten-doped tin oxide, titanium oxide-cerium oxide-tin oxide composite, titanium oxide- And a composite of tin oxide. The average particle size of the fine particles is about 1 to 100 nm, preferably 2 to 50 nm.

  Further, as other antistatic agents, acetylene black, Ketjen black, natural graphite, artificial graphite, titanium black, cationic type (quaternary ammonium salt, etc.), amphoteric ion type (betaine compound, etc.), anionic type (sulfonic acid, etc.) A homopolymer of a monomer having an ion conductive group of a nonionic type (glycerin or the like) or a copolymer of the monomer and another monomer, or an acrylate or methacrylate having a quaternary ammonium base A polymer having ionic conductivity such as a polymer having a site of origin; and a permanent antistatic agent of a type in which a hydrophilic polymer such as a polyethylene methacrylate copolymer is alloyed with an acrylic resin or the like.

≪Ionic compound≫
Further, as the ionic compound, an alkali metal salt and / or an organic cation-anion salt can be preferably used. As the alkali metal salt, an organic salt and an inorganic salt of the alkali metal can be used. In the present invention, the term "organic cation-anion salt" refers to an organic salt in which the cation part is composed of an organic substance, and the anion part may be an organic substance or an inorganic substance. There may be. "Organic cation-anion salt" is also referred to as ionic liquid or ionic solid.

<Alkali metal salt>
Examples of the alkali metal ion constituting the cation portion of the alkali metal salt include lithium, sodium, and potassium ions. Among these alkali metal ions, lithium ions are preferred.

The anion part of the alkali metal salt may be composed of an organic substance or an inorganic substance. Examples of the anion part constituting the organic salt include CH ₃ COO ⁻ , CF ₃ COO ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , and C ₄ F ₉ SO _{3. ^{-, C 3 F 7 COO -}} , (CF 3 SO 2) (CF 3 CO) N -, (FSO 2) 2 N-, - O 3 S (CF 2) 3 SO 3 -, PF 6 -, CO 3 ^2- , and the following general formulas (1) to (4),
_{(1) :( C n F 2n} + 1 SO 2) 2 N - ( where, n is an integer of from 1 to 10),
_{(2): CF 2 (C} m F 2m SO 2) 2 N - ( where, m is an integer of from 1 to 10),
^{_{(3): - O 3 S}} (CF 2) l SO 3 - ( where, l is an integer of from 1 to 10),
^{_{(4) :( C p F 2p}} + 1 SO 2) N - (C q F 2q + 1 SO 2), ( where, p, q is an integer of from 1 to 10), in represented by those such as are used. In particular, an anion portion containing a fluorine atom is preferably used because an ionic compound having good ion dissociation can be obtained. Examples of the anion portion constituting the inorganic salt include Cl ⁻ , Br ⁻ , I ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , NO ₃ ⁻ , AsF ₆ ⁻ , and SbF. ^{_{6 -, NbF 6 -, TaF}} 6 -, (CN) 2 N -, and the like can be used. As the anion moiety, (perfluoroalkylsulfonyl) imide represented by the general formula (1) such as (CF ₃ SO ₂ ) ₂ N ⁻ and (C ₂ F ₅ SO ₂ ) ₂ N ⁻ is preferable, and particularly ( (Trifluoromethanesulfonyl) imide represented by CF ₃ SO ₂ ) ₂ N ⁻ .

Specific examples of the organic salt of an alkali metal include sodium acetate, sodium alginate, sodium lignin sulfonate, sodium toluene sulfonate, LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, and Li (CF ₃ SO _2). ) ₂ N, Li (C ₂ F ₅ SO ₂ ) ₂ N, Li (C ₄ F ₉ SO ₂ ) ₂ N, Li (CF ₃ SO ₂ ) ₃ C, KO ₃ S (CF ₂ ) ₃ SO ₃ K, LiO ₃ S (CF ₂ ) ₃ SO ₃ K and the like, among which LiCF ₃ SO ₃ , Li (CF ₃ SO ₂ ) ₂ N, Li (C ₂ F ₅ SO ₂ ) ₂ N, Li (C ₄₎ F ₉ SO ₂ ) ₂ N, Li (CF ₃ SO ₂ ) ₃ C and the like are preferable, and Li (CF ₃ SO ₂ ) ₂ N, Li (C ₂ F ₅ SO ₂ ) ₂ N, Li (C ₄ F ₉ SO) _{2) 2} Fluorine-containing lithium imide salt is more preferably equal, particularly (perfluoroalkyl sulfonyl) imide lithium salts are preferred.

  In addition, examples of the inorganic salt of an alkali metal include lithium perchlorate and lithium iodide.

<Organic cation-anion salt>
The organic cation-anion salt used in the present invention is composed of a cation component and an anion component, and the cation component is an organic material. As the cation component, specifically, a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton, a cation having a pyrrole skeleton, an imidazolium cation, a tetrahydropyrimidinium cation, a dihydropyrimidinium cation, Examples include a pyrazolium cation, a pyrazolinium cation, a tetraalkylammonium cation, a trialkylsulfonium cation, and a tetraalkylphosphonium cation.

Examples of the anion component include Cl ⁻ , Br ⁻ , I ⁻ , AlCl ₄ ⁻ , Al ₂ Cl ₇ ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , ClO ₄ ⁻ , NO ₃ ⁻ , CH ₃ COO ⁻ , and CF ₃ COO. ⁻ , CH ₃ SO ₃ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ , AsF ₆ ⁻ , SbF ₆ ⁻ , NbF ₆ ⁻ , TaF ₆ ⁻ , (CN) ₂ N ⁻ , C ₄ F _{^{9 SO 3 -, C 3 F}} 7 COO -, ((CF 3 SO 2) (CF 3 CO) N -, (FSO 2) 2 N-, - O 3 S (CF 2) 3 SO 3 -, and the following General formulas (1) to (4),
_{(1) :( C n F 2n} + 1 SO 2) 2 N - ( where, n is an integer of from 1 to 10),
_{(2): CF 2 (C} m F 2m SO 2) 2 N - ( where, m is an integer of from 1 to 10),
_{^{(3): - O 3 S}} (CF 2) l SO 3 - ( where, l is an integer of from 1 to 10),
^{_{(4) :( C p F 2p}} + 1 SO 2) N - (C q F 2q + 1 SO 2), ( where, p, q is an integer of from 1 to 10), in represented by those such as are used. Among them, an anion component containing a fluorine atom is particularly preferably used because an ionic compound having good ion dissociation can be obtained.

  Examples of the ionic compound include, in addition to the alkali metal salt and the organic cation-anion salt, inorganic salts such as ammonium chloride, aluminum chloride, copper chloride, ferrous chloride, ferric chloride, and ammonium sulfate. . These ionic compounds can be used alone or in combination of two or more.

<Anchor layer>
As described above, the anchor layer is preferably formed to have a thickness of 0.01 to 0.5 μm and a surface resistance of 1 × 10 ⁸ to 1 × 10 ¹² Ω / □. The anchor layer can be formed from various antistatic composition. A conductive polymer is used as an antistatic agent for forming the anchor layer.

  Among these antistatic agents, conductive polymers are preferably used from the viewpoints of optical properties, appearance, antistatic effect, and stability of the antistatic effect when heated and humidified. In particular, conductive polymers such as polyaniline and polythiophene are preferably used. As the conductive polymer, those soluble in an organic solvent, water-soluble, or water-dispersible can be used as appropriate, but a water-soluble conductive polymer or a water-dispersible conductive polymer is preferably used. A water-soluble conductive polymer or a water-dispersible conductive polymer can be prepared as an aqueous solution or a water dispersion of a coating solution for forming an antistatic layer, and the coating solution does not need to use a non-aqueous organic solvent, and the organic This is because the deterioration of the optical film substrate due to the solvent can be suppressed. The aqueous solution or the aqueous dispersion can contain an aqueous solvent in addition to water. For example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert-amyl alcohol, 1-ethyl-1 Alcohols such as -propanol, 2-methyl-1-butanol, n-hexanol and cyclohexanol.

  Further, the water-soluble conductive polymer such as polyaniline and polythiophene or the water-dispersible conductive polymer preferably has a hydrophilic functional group in a molecule. Examples of the hydrophilic functional group include a sulfone group, an amino group, an amide group, an imino group, a quaternary ammonium base, a hydroxyl group, a mercapto group, a hydrazino group, a carboxyl group, a sulfate group, a phosphate group, and salts thereof. And the like. By having a hydrophilic functional group in the molecule, the compound becomes easily soluble in water or easily dispersed in water in the form of fine particles, so that the water-soluble conductive polymer or the water-dispersible conductive polymer can be easily prepared.

  Examples of commercially available water-soluble conductive polymers include polyaniline sulfonic acid (manufactured by Mitsubishi Rayon Co., Ltd., weight average molecular weight in terms of polystyrene of 150,000) and the like. Examples of commercially available water-dispersible conductive polymers include polythiophene-based conductive polymers (trade name, Denatron series, manufactured by Nagase Chemtech Co., Ltd.).

  Further, as a material for forming the anchor layer, a binder component can be added together with the conductive polymer for the purpose of improving the film forming property of the conductive polymer and the adhesion to the optical film. When the conductive polymer is an aqueous material of a water-soluble conductive polymer or a water-dispersible conductive polymer, a water-soluble or water-dispersible binder component is used. Examples of the binder include oxazoline group-containing polymer, polyurethane resin, polyester resin, acrylic resin, polyether resin, cellulose resin, polyvinyl alcohol resin, epoxy resin, polyvinylpyrrolidone, polystyrene resin, polyethylene glycol, Pentaerythritol and the like. Particularly, a polyurethane resin, a polyester resin, and an acrylic resin are preferable. One or two or more of these binders can be used according to the intended use.

The amount of the conductive polymer and the binder used depends on the type thereof, but is preferably controlled so that the surface resistance of the obtained anchor layer is 1 × 10 ⁸ to 1 × 10 ¹² Ω / □.

<First adhesive layer>
As described above, the first pressure-sensitive adhesive layer is preferably formed to have a thickness of 5 to 100 μm and a surface resistance of 1 × 10 ⁸ to 1 × 10 ¹² Ω / □. The first pressure-sensitive adhesive layer can be formed from a composition in which an antistatic agent is mixed with various pressure-sensitive adhesives.

  As the pressure-sensitive adhesive forming the first pressure-sensitive adhesive layer, various pressure-sensitive adhesives can be used, for example, a rubber-based pressure-sensitive adhesive, an acrylic-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, and a vinylalkylether-based pressure-sensitive adhesive. Agents, polyvinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, cellulose-based adhesives, and the like. An adhesive base polymer is selected according to the type of the adhesive. Among the pressure-sensitive adhesives, acrylic pressure-sensitive adhesives are preferably used because they are excellent in optical transparency, exhibit appropriate wettability, cohesiveness and adhesive pressure-sensitive adhesive properties, and are excellent in weather resistance and heat resistance. You.

  The acrylic pressure-sensitive adhesive contains a (meth) acrylic polymer as a base polymer. The (meth) acrylic polymer usually contains an alkyl (meth) acrylate as a main component as a monomer unit. In addition, (meth) acrylate means acrylate and / or methacrylate, and has the same meaning as (meth) in the present invention.

  Examples of the alkyl (meth) acrylate constituting the main skeleton of the (meth) acrylic polymer include those having a linear or branched alkyl group having 1 to 18 carbon atoms. These can be used alone or in combination. The average carbon number of these alkyl groups is preferably 3 to 9.

  In addition, from the viewpoints of adjustment of adhesive properties, durability, adjustment of retardation, adjustment of refractive index, etc., an alkyl (meth) acrylate containing an aromatic ring such as phenoxyethyl (meth) acrylate or benzyl (meth) acrylate is used. be able to.

  In the (meth) acrylic polymer, at least one kind having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group for the purpose of improving adhesiveness and heat resistance. Can be introduced by copolymerization. Specific examples of such a copolymerized monomer include, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6- (meth) acrylate. Hydroxyl-containing monomers such as -hydroxyhexyl, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate and (4-hydroxymethylcyclohexyl) -methyl acrylate Carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid; acid anhydrides such as maleic anhydride and itaconic anhydride Substance group-containing monomer; Caprolactone adduct of crylic acid; styrenesulfonic acid, allylsulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, (meth) acrylamidopropanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalene Sulfonic acid group-containing monomers such as sulfonic acid; and phosphoric group-containing monomers such as 2-hydroxyethylacryloyl phosphate.

  Also, (N-substituted) amides such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylolpropane (meth) acrylamide, etc. Monomers; alkylaminoalkyl (meth) acrylate monomers such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; (meth) acrylic Alkoxyalkyl (meth) acrylate-based monomers such as methoxyethyl methacrylate and ethoxyethyl (meth) acrylate; N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- ( (Meth) acryloyl-8-O Succinimide monomers such as cioctamethylene succinimide and N-acryloylmorpholine; maleimide monomers such as N-cyclohexylmaleimide and N-isopropylmaleimide, N-laurylmaleimide and N-phenylmaleimide; N-methylitaconimide and N-ethylitacon Imataconimide-based monomers such as imide, N-butylitaconimide, N-octylitaconimide, N-2-ethylhexylitaconimide, N-cyclohexylitaconimide, N-laurylitaconimide, and the like are also examples of the monomer for the modification purpose. .

  Further modifying monomers include vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinyl piperazine, vinyl pyrazine, vinyl pyrrole, vinyl imidazole, vinyl oxazole, vinyl morpholine, N- Vinyl-based monomers such as vinylcarboxylic acid amides, styrene, α-methylstyrene, N-vinylcaprolactam; cyanoacrylate-based monomers such as acrylonitrile and methacrylonitrile; epoxy-containing acrylic monomers such as glycidyl (meth) acrylate; Polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, methoxypoly (meth) acrylate Glycol-based acrylic ester monomers such as propylene glycol; and acrylate-based monomers such as tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate, silicone (meth) acrylate and 2-methoxyethyl acrylate can also be used. . Further, isoprene, butadiene, isobutylene, vinyl ether and the like can be mentioned.

  Further, as copolymerizable monomers other than those described above, silane-based monomers containing a silicon atom and the like can be mentioned. Examples of the silane monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, and 8-vinyloctyltrimethoxysilane. , 8-vinyloctyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltriethoxysilane, 10-acryloyloxydecyltriethoxysilane, and the like.

  Examples of the copolymerizable monomer include tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, Pentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate (Meth) acryloyl, such as esterified product of (meth) acrylic acid such as caprolactone-modified dipentaerythritol hexa (meth) acrylate and polyhydric alcohol And polyfunctional monomers having two or more unsaturated double bonds such as vinyl groups, and unsaturated functional groups such as (meth) acryloyl groups and vinyl groups in the skeleton of polyester, epoxy, urethane, etc. Polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, or the like to which two or more double bonds are added can also be used.

  The (meth) acryl-based polymer has an alkyl (meth) acrylate as a main component in the weight ratio of all constituent monomers, and the proportion of the copolymerized monomer in the (meth) acryl-based polymer is not particularly limited. The proportion of the monomer is preferably about 0 to 20%, about 0.1 to 15%, and more preferably about 0.1 to 10% in the weight ratio of all the constituent monomers.

  Among these copolymer monomers, a hydroxyl group-containing monomer and a carboxyl group-containing monomer are preferably used from the viewpoint of adhesiveness and durability. The hydroxyl group-containing monomer and the carboxyl group-containing monomer can be used in combination. When the pressure-sensitive adhesive composition contains a cross-linking agent, these copolymerized monomers serve as reaction points with the cross-linking agent. Since a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and the like have high reactivity with an intermolecular crosslinking agent, they are preferably used for improving the cohesiveness and heat resistance of the obtained pressure-sensitive adhesive layer. Hydroxyl group-containing monomers are preferred from the viewpoint of reworkability, and carboxyl group-containing monomers are preferred from the viewpoint of achieving both durability and reworkability.

  When a hydroxyl group-containing monomer is contained as a copolymerizable monomer, the proportion is preferably 0.01 to 15% by weight, more preferably 0.03 to 10% by weight, and further preferably 0.05 to 7% by weight. . When a carboxyl group-containing monomer is contained as a copolymerizable monomer, the proportion is preferably 0.05 to 10% by weight, more preferably 0.1 to 8% by weight, and further preferably 0.2 to 6% by weight. .

  The (meth) acrylic polymer of the present invention generally has a weight average molecular weight in the range of 500,000 to 3,000,000. Considering durability, especially heat resistance, it is preferable to use those having a weight average molecular weight of 700,000 to 2.7 million. More preferably, it is 800,000 to 2.5 million. If the weight average molecular weight is less than 500,000, it is not preferable in terms of heat resistance. On the other hand, if the weight average molecular weight is more than 3,000,000, a large amount of a diluting solvent is required to adjust the viscosity for coating, which is not preferable because the cost is increased. The weight average molecular weight is a value measured by GPC (gel permeation chromatography) and calculated in terms of polystyrene.

  For the production of such a (meth) acrylic polymer, known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various types of radical polymerization can be appropriately selected. The (meth) acrylic polymer obtained may be any of a random copolymer, a block copolymer, a graft copolymer and the like.

  As the antistatic agent used for forming the first pressure-sensitive adhesive layer, an ionic compound is preferable among the above examples from the viewpoint of compatibility with the base polymer and transparency of the pressure-sensitive adhesive layer. In particular, when an acrylic pressure-sensitive adhesive having a (meth) acrylic polymer as a base polymer is used, it is preferable to use an ionic compound. As the ionic compound, an ionic liquid is preferable from the viewpoint of an antistatic function.

The amount of the pressure-sensitive adhesive and antistatic agent used is controlled so that the surface resistance value of the obtained first pressure-sensitive adhesive layer is 1 × 10 ⁸ to 1 × 10 ¹² Ω / □, although it depends on the kind of the pressure-sensitive adhesive and the antistatic agent. You. For example, it is preferable to use 0.05 to 20 parts by weight of an antistatic agent (for example, in the case of an ionic compound) with respect to 100 parts by weight of the base polymer (for example, (meth) acrylic polymer) of the pressure-sensitive adhesive. It is preferable to use the antistatic agent in an amount of 0.05 part by weight or more from the viewpoint of improving the antistatic performance. Further, the amount of the antistatic agent (B) is preferably at least 0.1 part by weight, more preferably at least 0.5 part by weight. For satisfying the durability, it is preferably used in an amount of 20 parts by weight or less, more preferably 10 parts by weight or less.

  The pressure-sensitive adhesive composition forming the first pressure-sensitive adhesive layer may contain a crosslinking agent according to the base polymer. When, for example, a (meth) acrylic polymer is used as the base polymer, an organic crosslinking agent or a polyfunctional metal chelate can be used as the crosslinking agent. Examples of the organic crosslinking agent include an isocyanate crosslinking agent, a peroxide crosslinking agent, an epoxy crosslinking agent, and an imine crosslinking agent. Multifunctional metal chelates are those in which a polyvalent metal is covalently or coordinated with an organic compound. Examples of the polyvalent metal atom include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, and Ti. No. The atom in the organic compound which forms a covalent bond or a coordinate bond includes an oxygen atom and the like, and the organic compound includes an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, a ketone compound and the like.

  The amount of the crosslinking agent to be used is preferably 3 parts by weight or less, more preferably 0.01 to 3 parts by weight, further preferably 0.02 to 2 parts by weight, based on 100 parts by weight of the (meth) acrylic polymer. And more preferably 0.03 to 1 part by weight.

  The pressure-sensitive adhesive composition for forming the first pressure-sensitive adhesive layer can contain a silane coupling agent and other additives. For example, polyalkylene glycol polyether compounds such as polypropylene glycol, powders such as colorants and pigments, dyes, surfactants, plasticizers, tackifiers, surface lubricants, leveling agents, softeners, antioxidants , An anti-aging agent, a light stabilizer, an ultraviolet absorber, a polymerization inhibitor, an inorganic or organic filler, a metal powder, particles, a foil, and the like can be appropriately added according to the intended use. Further, a redox system to which a reducing agent is added may be employed within a controllable range. These additives are preferably used in an amount of 5 parts by weight or less, more preferably 3 parts by weight or less, and further preferably 1 part by weight or less based on 100 parts by weight of the (meth) acrylic polymer.

<Surface treatment layer>
The surface treatment layer can be provided on the side of the first polarizing film on which the anchor layer is not provided. The surface treatment layer can be provided on the transparent protective film used for the first polarizing film, or can be separately provided separately from the transparent protective film. As the surface treatment layer, a hard coat layer, an anti-glare treatment layer, an anti-reflection layer, an anti-sticking layer, and the like can be provided.

  The surface treatment layer is preferably a hard coat layer. As a material for forming the hard coat layer, for example, a thermoplastic resin, a material which is cured by heat or radiation, or the like can be used. Examples of the material include radiation curable resins such as thermosetting resins, ultraviolet curable resins, and electron beam curable resins. Among these, an ultraviolet-curable resin that can efficiently form a cured resin layer with a simple processing operation in a curing treatment by ultraviolet irradiation is preferable. These curable resins include various resins such as polyester, acrylic, urethane, amide, silicone, epoxy, and melamine resins, and include these monomers, oligomers, and polymers. In particular, a radiation-curable resin, particularly an ultraviolet-curable resin, is preferable because of its high processing speed and little heat damage to the substrate. The UV-curable resin preferably used is, for example, a resin having a UV-polymerizable functional group, among which a resin containing an acrylic monomer or oligomer component having two or more, particularly 3 to 6, functional groups is mentioned. Further, a photopolymerization initiator is blended in the ultraviolet curable resin.

  Further, as the surface treatment layer, an antiglare treatment layer or an antireflection layer for the purpose of improving visibility can be provided. Further, an antiglare treatment layer and an antireflection layer can be provided on the hard coat layer. The constituent material of the antiglare layer is not particularly limited, and for example, a radiation-curable resin, a thermosetting resin, a thermoplastic resin, or the like can be used. As the antireflection layer, titanium oxide, zirconium oxide, silicon oxide, magnesium fluoride, or the like is used. A plurality of antireflection layers can be provided. In addition, examples of the surface treatment layer include an anti-sticking layer.

  The surface treatment layer can be provided with conductivity by containing an antistatic agent. As the antistatic agent, those described above can be used.

<Surface protection film>
The surface protection film that can be provided on the surface treatment layer (the first polarization film is intended for the first polarization film when the first polarization film does not have a surface treatment layer, the same applies hereinafter) includes a pressure-sensitive adhesive layer on at least one surface of the support film. Can be used. The pressure-sensitive adhesive layer of the surface protective film may contain a light release agent, an antistatic agent and the like. When the pressure-sensitive adhesive layer of the surface protective film contains an antistatic agent, the surface protective film is attached to the surface treatment layer, and then, by peeling, does not contain an antistatic agent. A conductive function can be imparted to the surface of the surface treatment layer, and the surface treatment layer can contain an antistatic agent. The same antistatic agent as described above can be used. Further, in order to impart a conductive function to the surface of the surface treatment layer by peeling the surface protective film, it is preferable to use a light release agent together with an antistatic agent in the pressure-sensitive adhesive layer of the surface protective film. Examples of the light release agent include polyorganosiloxane and the like. The degree to which the conductive function is imparted to the surface of the surface treatment layer is determined by appropriately adjusting the amounts of the charged conductive agent and the light release agent. In addition, the surface protective film may be provided on a second polarizing film surface described later.

<Other layers>
In the polarizing film with a pressure-sensitive adhesive layer of the present invention, in addition to the above-described layers, an easy-adhesion layer may be provided on the surface of the first polarizing film on the side where the anchor layer is provided, or various kinds of easy-adhesion such as corona treatment and plasma treatment may be performed. Treatment.

  Hereinafter, the in-cell type liquid crystal cell B and the in-cell type liquid crystal panel C will be described.

(In-cell type liquid crystal cell B)
As shown in FIGS. 2 to 6, the in-cell type liquid crystal cell B includes a liquid crystal layer 20 containing liquid crystal molecules that are homogeneously aligned in the absence of an electric field, a first transparent substrate 41 sandwiching the liquid crystal layer 20 on both sides, and a second liquid crystal cell B. It has two transparent substrates 42. In addition, a touch sensing electrode unit related to a touch sensor and a touch drive function is provided between the first transparent substrate 41 and the second transparent substrate 42.

  The touch sensing electrode unit may be formed by a touch sensor electrode 31 and a touch drive electrode 32, as shown in FIGS. Here, the touch sensor electrode refers to a touch detection (reception) electrode. The touch sensor electrode 31 and the touch drive electrode 32 can be independently formed in various patterns. For example, when the in-cell type liquid crystal cell B is a plane, it can be arranged in a pattern that intersects at right angles by a form provided independently in the X-axis direction and the Y-axis direction. In FIGS. 2, 3, and 6, the touch sensor electrode 31 is disposed closer to the first transparent substrate 41 (viewing side) than the touch drive electrode 32. The touch drive electrode 32 may be disposed on the first transparent substrate 41 side (viewing side) with respect to the touch sensor electrode 31.

  On the other hand, as shown in FIGS. 4 and 5, the touch sensing electrode unit may use an electrode 33 integrally formed with a touch sensor electrode and a touch drive electrode.

  In addition, the touch sensing electrode unit may be disposed between the liquid crystal layer 20 and the first transparent substrate 41 or the second transparent substrate 42. FIGS. 2 and 4 show a case where the touch sensing electrode unit is disposed between the liquid crystal layer 20 and the first transparent substrate 41 (on the viewing side of the liquid crystal layer 20). 3 and 5 show a case where the touch sensing electrode unit is disposed between the liquid crystal layer 20 and the second transparent substrate 42 (on the backlight side with respect to the liquid crystal layer 20).

  In addition, as shown in FIG. 6, the touch sensing electrode unit has a touch sensor electrode 31 between the liquid crystal layer 20 and the first transparent substrate 41, and the liquid crystal layer 20 and the second transparent substrate 42 A touch drive electrode 32 can be provided between the two.

  The drive electrodes (the touch drive electrodes 32, the touch sensor electrodes, and the electrodes 33 integrally formed with the touch drive electrodes) in the touch sensing electrode portion can be used also as common electrodes for controlling the liquid crystal layer 20.

  As the liquid crystal layer 20 used in the in-cell type liquid crystal cell B, a liquid crystal layer containing liquid crystal molecules homogeneously aligned in the absence of an electric field is used. As the liquid crystal layer 20, for example, an IPS liquid crystal layer is preferably used. In addition, as the liquid crystal layer 20, any type of liquid crystal layer such as TN type, STN type, π type, and VA type can be used. The thickness of the liquid crystal layer 20 is, for example, about 1.5 μm to 4 μm.

As described above, the in-cell type liquid crystal cell B has a touch sensor and a touch sensing electrode portion related to a touch driving function in the liquid crystal cell, and does not have a touch sensor electrode outside the liquid crystal cell. That is, a conductive layer (surface resistance value is 1 × 10 ¹³ Ω /) on the viewing side of the first transparent substrate 41 of the in-cell type liquid crystal cell B (the liquid crystal cell side of the first adhesive layer 2 of the in-cell type liquid crystal panel C). □) is not provided. In addition, in the in-cell type liquid crystal panel C shown in FIGS. 2 to 6, the order of each configuration is shown, but the in-cell type liquid crystal panel C can have other configurations as appropriate. A color filter substrate can be provided on the liquid crystal cell (first transparent substrate 41).

  The material forming the transparent substrate includes, for example, glass or a polymer film. Examples of the polymer film include polyethylene terephthalate, polycycloolefin, and polycarbonate. When the transparent substrate is formed of glass, its thickness is, for example, about 0.1 mm to 1 mm. When the transparent substrate is formed of a polymer film, its thickness is, for example, about 10 μm to 200 μm. The transparent substrate may have an easily adhesive layer or a hard coat layer on the surface.

  The touch sensor electrode 31 (capacitance sensor), the touch drive electrode 32, or the electrode 33 integrally formed with the touch sensor electrode and the touch drive electrode, which form the touch sensing electrode portion, are formed as a transparent conductive layer. The constituent material of the transparent conductive layer is not particularly limited, and includes, for example, metals such as gold, silver, copper, platinum, palladium, aluminum, nickel, chromium, titanium, iron, cobalt, tin, magnesium, tungsten, and the like. Alloys and the like. Further, examples of the constituent material of the transparent conductive layer include metal oxides of indium, tin, zinc, gallium, antimony, zirconium, and cadmium, and specifically, indium oxide, tin oxide, titanium oxide, cadmium oxide and And the like. In addition, other metal compounds made of copper iodide or the like are used. The metal oxide may further include an oxide of a metal atom shown in the above group, if necessary. For example, indium oxide (ITO) containing tin oxide, tin oxide containing antimony, and the like are preferably used, and ITO is particularly preferably used. It is preferable that ITO contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.

  The electrodes (the touch sensor electrode 31, the touch drive electrode 32, the electrode 33 integrally formed with the touch sensor electrode and the touch drive electrode) related to the touch sensing electrode unit are usually provided with the first transparent substrate 41 and / or the second transparent substrate. A transparent electrode pattern can be formed inside the substrate 42 (on the side of the liquid crystal layer 20 in the in-cell type liquid crystal cell B) by a conventional method. The transparent electrode pattern is usually electrically connected to a lead line (not shown) formed at an end of the transparent substrate, and the lead line is connected to a controller IC (not shown). As the shape of the transparent electrode pattern, an arbitrary shape such as a stripe shape or a rhombus shape, other than a comb shape, can be adopted depending on the application. The height of the transparent electrode pattern is, for example, 10 nm to 100 nm, and the width is 0.1 mm to 5 mm.

(In-cell type liquid crystal panel C)
2 to 6, the in-cell type liquid crystal panel C of the present invention has a polarizing film A with an adhesive layer on the viewing side of the in-cell type liquid crystal cell B, and has a second polarizing film 11 on the opposite side. be able to. The polarizing film A with the pressure-sensitive adhesive layer is disposed on the first transparent substrate 41 side of the in-cell type liquid crystal cell B via the first pressure-sensitive adhesive layer 2 without a conductive layer. On the other hand, on the side of the second transparent substrate 42 of the in-cell type liquid crystal cell B, a second polarizing film 11 is disposed via a second adhesive layer 12. The first polarizing film 1 and the second polarizing film 11 in the polarizing film A with an adhesive layer are arranged on both sides of the liquid crystal layer 20 such that the transmission axes (or absorption axes) of the respective polarizers are orthogonal to each other.

  As the second polarizing film 11, those described for the first polarizing film 1 can be used. The second polarizing film 11 may be the same as or different from the first polarizing film 1.

  For forming the second pressure-sensitive adhesive layer 12, the pressure-sensitive adhesive described for the first pressure-sensitive adhesive layer 2 can be used. As the pressure-sensitive adhesive used for forming the second pressure-sensitive adhesive layer 12, the same pressure-sensitive adhesive as that of the first pressure-sensitive adhesive layer 2 may be used, or a different pressure-sensitive adhesive may be used. The thickness of the second pressure-sensitive adhesive layer 12 is not particularly limited, and is, for example, about 1 to 100 μm. Preferably, it is 2 to 50 μm, more preferably 2 to 40 μm, and still more preferably 5 to 35 μm.

  In the in-cell type liquid crystal panel C, a conductive structure 50 can be provided on the side surfaces of the anchor layer 3 and the first adhesive layer 2 of the polarizing film A with the adhesive layer. The conductive structure 50 may be provided on all of the side surfaces of the anchor layer 3 and the first pressure-sensitive adhesive layer 2 or may be provided on a part thereof. When the conductive structure is provided in a part, the conductive structure is provided in an area of 1% by area or more, preferably 3% by area or more of the area of the side surface in order to secure conduction on the side surface. preferable. In addition to the above, as shown in FIG. 2, a conductive material 51 can be provided on the side surfaces of the first polarizing film 1 and the surface treatment layer 4.

  With the conductive structure 50, the generation of static electricity can be suppressed by connecting a potential from the side surfaces of the anchor layer 3 and the first pressure-sensitive adhesive layer 2 to other suitable locations. As a material for forming the conductive structures 50 and 51, for example, a conductive paste such as silver, gold, or another metal paste can be used, and a conductive adhesive or any other suitable conductive material can be used. . The conductive structure 50 may be formed in a linear shape extending from the side surfaces of the anchor layer 3 and the first pressure-sensitive adhesive layer 2. The conductive structure 51 can also be formed in a similar linear shape.

  In addition, the first polarizing film 1 disposed on the viewing side of the liquid crystal layer 20 and the second polarizing film 11 disposed on the side opposite to the viewing side of the liquid crystal layer 20 may have other positions depending on the suitability of the respective positions. Optical films can be laminated and used. Examples of the other optical film include liquid crystal display devices such as a reflection plate, an anti-transmission plate, a retardation film (including a wavelength plate such as １ ／ and １ ／), a visual compensation film, and a brightness enhancement film. And an optical layer which may be used for the above. These can be used as one layer or two or more layers.

(Liquid crystal display)
In the liquid crystal display device with a built-in touch sensing function using the in-cell type liquid crystal panel C of the present invention, a member forming the liquid crystal display device such as one using a backlight or a reflector in an illumination system can be appropriately used.

  Hereinafter, the present invention will be described specifically with reference to Production Examples and Examples, but the present invention is not limited to these Examples. In addition, all parts and% in each example are based on weight. The room temperature leaving conditions not particularly specified below are all 23 ° C. and 65% RH.

<Measurement of weight average molecular weight of (meth) acrylic polymer>
The weight average molecular weight (Mw) of the (meth) acrylic polymer was measured by GPC (gel permeation chromatography). Mw / Mn was measured similarly.
・ Analyzer: Tosoh Corporation, HLC-8120GPC
-Column: Tosoh Corporation, G7000H _XL + GMH _XL + GMH _XL
・ Column size: 7.8mmφ × 30cm each 90cm in total
-Column temperature: 40 ° C
・ Flow rate: 0.8 mL / min
・ Injection volume: 100 μL
・ Eluent: tetrahydrofuran ・ Detector: differential refractometer (RI)
・ Standard sample: polystyrene

<Preparation of polarizing film>
A polyvinyl alcohol film having a thickness of 80 μm was stretched up to 3 times while being dyed in a 0.3% iodine solution at 30 ° C. for 1 minute between rolls having different speed ratios. Thereafter, the film was stretched to a total stretch ratio of 6 times while immersing it in an aqueous solution containing boric acid at 4% concentration, 10% concentration of potassium iodide at 60 ° C for 0.5 minute. Next, after washing by immersion in an aqueous solution containing 1.5% concentration of potassium iodide at 30 ° C. for 10 seconds, drying was performed at 50 ° C. for 4 minutes to obtain a polarizer having a thickness of 30 μm. A saponified triacetyl cellulose film having a thickness of 80 μm was bonded to both surfaces of the polarizer with a polyvinyl alcohol-based adhesive to form a polarizing film.

<Formation of surface treatment layer>
100 parts of a UV-curable acrylic resin (manufactured by Dainippon Ink and Chemicals, Unidick 17-806), 3 parts of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals, Irgacure 184) and 100 parts of toluene A coat resin composition (coating liquid) was prepared. The coating liquid was applied to one surface of the polarizing film obtained above using a wire bar, and then heated and dried at 80 ° C. for 1 minute to form a coating film. Next, the coating film was irradiated with ultraviolet rays of 300 mJ / cm ^{2 by} a metal halide lamp to cure the coating film and form a hard coat layer having a thickness of 5 μm.

(Preparation of forming material for anchor layer)
8.6 parts of a solution containing a thiophene-based polymer in a solid content of 10 to 50% by weight (trade name: Denatron P-580W, manufactured by Nagase ChemteX Corporation), a solution containing an oxazoline group-containing acrylic polymer (trade name: Epocross) One part of WS-700 (produced by Nippon Shokubai Co., Ltd.) and 90.4 parts of water were mixed to prepare a coating solution for forming an anchor layer having a solid concentration of 0.5% by weight. The obtained coating solution for forming an anchor layer contained 0.04% by weight of a polythiophene-based polymer and 0.25% by weight of an oxazoline group-containing acrylic polymer.

(Formation of anchor layer)
The coating liquid for forming an anchor layer is applied to one surface of the polarizing film (the side on which the hard coat layer is not provided) so that the thickness after drying is as shown in Table 1, and dried at 80 ° C. for 2 minutes. To form an anchor layer. The obtained anchor layer contained 8% by weight and 50% by weight of a thiophene-based polymer and an oxazoline group-containing acrylic polymer, respectively.

(Preparation of acrylic polymer)
In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, 74.8 parts of butyl acrylate, 23 parts of phenoxyethyl acrylate, 0.5 part of N-vinyl-2-pyrrolidone (NVP), A monomer mixture containing 0.3 parts of acrylic acid and 0.4 parts of 4-hydroxybutyl acrylate was charged. Further, 0.1 part of 2,2′-azobisisobutyronitrile as a polymerization initiator was charged together with 100 parts of ethyl acetate with respect to 100 parts of the monomer mixture (solid content), and nitrogen gas was added with gentle stirring. After introducing and purging with nitrogen, a polymerization reaction was carried out for 8 hours while maintaining the liquid temperature in the flask at around 55 ° C. to obtain a solution of an acrylic polymer having a weight average molecular weight (Mw) of 1.6 million and Mw / Mn = 3.7. Was prepared.

(Preparation of adhesive composition)
With respect to 100 parts of the solid content of the solution of the acrylic polymer obtained above, lithium (bis (trifluoromethanesulfonyl) imide) manufactured by Mitsubishi Materials Corporation was blended as an ionic compound in an amount shown in Table 1, and further, 0.1 part of isocyanate crosslinking agent (Takenate D160N manufactured by Mitsui Chemicals, Trimethylolpropane hexamethylene diisocyanate), 0.3 part of benzoyl peroxide (Niper BMT manufactured by NOF Corporation) and γ-glycidoxypropylmethoxysilane ( (Shin-Etsu Chemical Co., Ltd .: KBM-403) 0.2 part was blended to prepare a solution of an acrylic pressure-sensitive adhesive composition.

(Formation of adhesive layer)
Then, the solution of the acrylic pressure-sensitive adhesive composition was coated on one side of a polyethylene terephthalate film (separator film: MRF38, manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) treated with a silicone-based release agent to form a dried pressure-sensitive adhesive layer. It was applied to a thickness shown in Table 1 and dried at 155 ° C. for 1 minute to form an adhesive layer on the surface of the separator film. The pressure-sensitive adhesive layer was transferred to a polarizing film having an anchor layer or a polarizing film having no anchor layer.

Examples 1 to 11 and Comparative Examples 1 to 4
An anchor layer and a pressure-sensitive adhesive layer were sequentially formed on one surface (the side on which the hard coat layer was not provided) of the polarizing film obtained above by the combinations shown in Table 1 to prepare a polarizing film with a pressure-sensitive adhesive layer. .

  In Example 11, an antistatic layer was provided by bonding the following surface protective film to the hard coat layer side of the obtained polarizing film with an adhesive layer and then peeling it off.

<Preparation of surface protection film>
A (meth) acrylic polymer (A) and a pressure-sensitive adhesive solution shown below were prepared, and a surface protective film was prepared by the following method using the pressure-sensitive adhesive solution.

[Preparation of (meth) acrylic polymer (A)]
100 parts of 2-ethylhexyl acrylate (2EHA), 10 parts of 4-hydroxybutyl acrylate (4HBA), and 0.02 of acrylic acid (AA) were placed in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser. Parts, 2,2′-azobisisobutyronitrile 0.2 parts as a polymerization initiator and 157 parts of ethyl acetate were charged, and nitrogen gas was introduced with gentle stirring, and the liquid temperature in the flask was kept at about 65 ° C. The polymerization reaction was carried out for 6 hours while keeping the temperature, to prepare a (meth) acrylic polymer (A) solution (40% by weight). The acrylic polymer (A) had a weight average molecular weight of 540,000 and a glass transition temperature (Tg) of -67 ° C.

(Preparation of adhesive solution)
The (meth) acrylic polymer (A) solution (40%) is diluted to 20% with ethyl acetate, and 500 parts (solid content: 100 parts) of this solution is mixed with an organopolysiloxane having an oxyalkylene chain as a silicone component ( KF-353, manufactured by Shin-Etsu Chemical Co., Ltd.) was diluted to 10% with ethyl acetate (2 parts, solid content: 0.2 parts), and lithium bis (trifluoro) was used as an alkali metal salt (ionic compound) as an antistatic agent. 15 parts (solid content: 0.15 part) of a solution obtained by diluting romethanesulfonyl) imide (LiN (CF ₃ SO ₂ ) ₂ : LiTFSI, manufactured by Tokyo Chemical Industry Co., Ltd.) with ethyl acetate to 15% (solid content: 0.15 part); 1.75 parts by weight of isocyanurate of hexamethylene diisocyanate (Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.) .75 parts by weight) 0.3 part (solid content 0.3 part) of 1,3-bis (isocyanatomethyl) cyclohexane (manufactured by Mitsui Chemicals, Inc., Takenate 600) which is a bifunctional isocyanate compound, and dilauric acid as a crosslinking catalyst 2 parts of dibutyltin (1% ethyl acetate solution) (solid content: 0.02 parts) were added, and mixed and stirred to prepare an acrylic pressure-sensitive adhesive solution.

(Preparation of antistatic treatment film)
The antistatic agent solution was prepared by diluting 10 parts of an antistatic agent (Microsolver RMd-142, manufactured by Solvex Corporation, mainly composed of tin oxide and a polyester resin) with a mixed solvent consisting of 30 parts of water and 70 parts of methanol. Prepared.

  The obtained antistatic agent solution was applied to a polyethylene terephthalate (PET) film (thickness: 38 μm) using a Meyer bar, and dried at 130 ° C. for 1 minute to remove the solvent and remove the antistatic layer (thickness). (0.2 μm) to form an antistatic treatment film.

[Production of surface protection film (adhesive sheet)]
The acrylic pressure-sensitive adhesive solution was applied to the surface of the antistatic treatment film opposite to the antistatic treatment surface, and heated at 130 ° C. for 2 minutes to form a 15 μm-thick pressure-sensitive adhesive layer. Next, a silicone-treated surface of a polyethylene terephthalate film (thickness: 25 μm) having one surface subjected to silicone treatment was bonded to the surface of the pressure-sensitive adhesive layer to prepare a surface protective film.

In Comparative Example 1, the conductive polymer was not blended in the coating solution for forming the anchor layer.
In Comparative Examples 2 and 3, no ionic compound was blended in the preparation of the pressure-sensitive adhesive composition.

The anchor layer of Comparative Example 4 was formed as follows.
100 g of dipentaerythritol hexaacrylate, 10 g of a photoinitiator (Irgacure 184, manufactured by Ciba Specialty Chemicals), 100 g of methyl alcohol, and 100 g of propylene glycol monomethyl ether (PGM) are sufficiently blended and mixed with a stirrer so as to be uniformly mixed. Stir for about 1 hour. Next, while gradually dropping 40 g of the AZO dispersion liquid into the prepared stirring liquid, the mixture was stirred for about 1 hour so as to be sufficiently mixed to prepare a coating liquid. Thereafter, the prepared coating solution was coated on a triacetyl cellulose film using a bar coater such that the thickness after curing became 4 μm, and the coated film was dried in a 60 ° C. oven for 2 minutes. Next, an anchor layer was formed by irradiating the dried film with a medium pressure mercury lamp (UV source, light amount: 1 J / cm ² ) to cure the film.

  The following evaluation was performed about the polarizing film with an adhesive layer obtained by the said Example and the comparative example. Table 1 shows the evaluation results.

<Surface resistance (Ω / □): conductivity>
The surface resistance of the anchor layer, the pressure-sensitive adhesive layer, and the surface treatment layer was measured.
The surface resistance value of the anchor layer was measured on the surface of the polarizing film with the anchor layer on the anchor layer side before the formation of the pressure-sensitive adhesive layer.
The surface resistance value of the pressure-sensitive adhesive layer was measured on the surface of the pressure-sensitive adhesive layer formed on the separator film.
The surface resistance value of the surface treatment layer was measured for the surface treatment layer of the polarizing film provided with the pressure-sensitive adhesive layer. In Example 11, the surface resistance value of the surface treatment layer was measured after bonding the surface protective film to the polarizing film provided with the pressure-sensitive adhesive layer and then peeling it off.
After the separator film was peeled off from the obtained polarizing film with an adhesive layer, the surface resistance value of the surface of the adhesive layer was measured. The measurement was performed using MCP-HT450 manufactured by Mitsubishi Chemical Analytech. The measurement results are shown at the top of the cells in Table 1 where other evaluation items are described.

<ESD test>
After the separator film was peeled off from the polarizing film with the pressure-sensitive adhesive layer, as shown in FIG. 2 or FIG. 3, it was bonded to the viewing side of the in-cell type liquid crystal cell. Next, a silver paste having a width of 5 mm was applied to the side surfaces of the laminated polarizing film so as to cover the respective side surfaces of the hard coat layer, the polarizing film, the anchor layer, and the adhesive layer, and connected to an external ground electrode. . The time until the liquid crystal display panel is set on a backlight device, an electrostatic discharge gun (Electrostatic discharge Gun) is fired at an applied voltage of 10 kV onto the polarizing film surface on the viewing side, and the white spot disappears due to electricity. Was measured and judged according to the following criteria. However, in Example 1, the conductive structure was not formed using the silver paste.
(Evaluation criteria)
A: Within 1 second.
A: Within 3 seconds.
〇: Over 3 seconds to within 5 seconds.
Δ: More than 5 seconds and less than 20 seconds.
X: Over 20 seconds.

<TSP sensitivity>
A wiring (not shown) around the transparent electrode pattern inside the in-cell type liquid crystal cell was connected to a controller IC (not shown) to produce a liquid crystal display device with a built-in touch sensing function. Visual observation was performed while using the input display device of the liquid crystal display device with a built-in touch sensing function to confirm the presence or absence of malfunction.
〇: No malfunction.
×: Malfunction occurred.

<TSP sensitivity under humidification>
After the liquid crystal display device with a built-in touch sensing function was put in a humidified atmosphere of 60 ° C./90% RH for 120 hours, the TSP sensitivity was confirmed in a humidified atmosphere.

<Humidification durability test>
What cut | disconnected the polarizing film with an adhesive layer in 15-inch size was used as the sample. The sample was adhered to a 0.7 mm-thick alkali-free glass (manufactured by Corning, EG-XG) using a laminator.
Then, the sample was autoclaved at 50 ° C. and 0.5 MPa for 15 minutes to completely adhere the sample to the alkali-free glass. After the sample subjected to such a treatment was subjected to a treatment in an atmosphere of 60 ° C./90% RH for 500 hours, the appearance between the polarizing film and the alkali-free glass was visually evaluated according to the following criteria.
(Evaluation criteria)
A: No change in appearance such as foaming and peeling was observed.
：: Slight peeling or foaming at the end, but no practical problem.
Δ: Peeling or foaming at the end, but no practical problem unless it is a special use.
X: There is significant peeling at the end, and there is a problem in practical use.

表１中、Ｌｉ‐ＴＦＳＩはビス（トリフルオロメタンスルホニル）イミド リチウムを示す。

In Table 1, Li-TFSI indicates lithium bis (trifluoromethanesulfonyl) imide.

Reference Signs List A polarizing film with adhesive layer B in-cell type liquid crystal cell C in-cell type liquid crystal panel 1, 11 first, second polarizing film 2, 12 first, second adhesive layer 3 anchor layer 4 surface treatment layer 20 liquid crystal layer 31 touch Sensor electrode 32 Touch drive electrode 33 Touch drive electrode and sensor electrode 41, 42 First and second transparent substrates

Claims (10)

A liquid crystal layer containing liquid crystal molecules homogeneously aligned in the absence of an electric field, a first transparent substrate and a second transparent substrate sandwiching the liquid crystal layer on both sides, and between the first transparent substrate and the second transparent substrate. In-cell type liquid crystal cell having a touch sensor and a touch sensing electrode unit according to a touch drive function,
An in-cell type liquid crystal panel having a polarizing film with an adhesive layer disposed on a first transparent substrate side on a viewing side of the in-cell type liquid crystal cell without a conductive layer via a first adhesive layer,
The pressure-sensitive adhesive layer-attached polarizing film has a first polarizing film, an anchor layer, and a first pressure-sensitive adhesive layer in this order,
The anchor layer contains a conductive polymer, the first pressure-sensitive adhesive layer contains an antistatic agent ,
The anchor layer has a thickness of 0.01 to 0.5 μm and a surface resistance of 1 × 10 ⁸ to 1 × 10 ¹² Ω / □,
The first pressure-sensitive adhesive layer has a thickness of 5 to 100 μm, a surface resistance of 1 × 10 ⁸ to 1 × 10 ¹² Ω / □, and
Cell type liquid crystal panel surface resistance of the pressure-sensitive adhesive layer side of the pressure-sensitive adhesive layer-attached polarizing film and said ^{1 × 10 8 ~1 × 10 11} Ω / □ der Rukoto.   The in-cell type liquid crystal panel according to claim 1, wherein a conductive structure is provided on side surfaces of the anchor layer and the first pressure-sensitive adhesive layer of the pressure-sensitive adhesive layer-attached polarizing film. 3. The in-cell type liquid crystal panel according to claim 1, wherein the antistatic agent is an alkali metal salt and / or an organic cation-anion salt. The touch sensing electrode unit, in-cell type liquid crystal panel according to any one of claims 1 to 3, characterized in that it is disposed between said liquid crystal layer first transparent substrate or the second transparent substrate. The in-cell type liquid crystal panel according to claim 4, wherein the touch sensing electrode unit is disposed between the liquid crystal layer and the first transparent substrate. The in-cell type liquid crystal panel according to claim 4, wherein the touch sensing electrode unit is disposed between the liquid crystal layer and the second transparent substrate. The in-cell type liquid crystal panel according to any one of claims 1 to 6 , wherein the touch sensing electrode unit is formed by a touch sensor electrode and a touch drive electrode. The in-cell type liquid crystal panel according to any one of claims 4 to 6 , wherein the touch sensing electrode portion of the in-cell type liquid crystal cell is an electrode in which a touch sensor electrode and a touch drive electrode are integrally formed. The in-cell type liquid crystal according to any one of claims 1 to 8 , further comprising a second polarizing film disposed on a side of the second transparent substrate of the in-cell type liquid crystal cell via a second adhesive layer. panel. A liquid crystal display device having the in-cell liquid crystal panel according to claim 9 .

Images